Synthesis of silylmetallic complexes

ABSTRACT

SILYL COMPLEXES OF PLATINUM AND PALLADIUM ARE PREPARED BY REACTING BELOW 150* C. DISILANES OR HYDROSILANES WITH PHOSPHINE COMPLEXES OF THE FORMULA M(PR&#39;&#39;3)2Y2. SPECIFICALLY HEXACHLORODISILANE IS REACTED WITH   PD(PPHME2)2CL2   TO GIVE PD(PPHME2)2(SICL3)CL AND/OR   PD(PPHME2)2(SICL3)2.

United States Patent 3,746,732 SYNTHESIS OF SILYLMETALLIC COMPLEXESWilliam H. Atwell and Gary N. Bokerman, Midland,

Mich., assignors to Dow Corning Corporation, Midland, Mich. No Drawing.Filed Dec. 15, 1971, Ser. No. 208,414 Int. Cl. C07b 15/00 U.S. Cl.260-429 R 8 Claims ABSTRACT OF THE DISCLOSURE Silyl complexes ofplatinum and palladium are prepared by reacting below 150 C. disilanesor hydrosilanes with phosphine complexes of the formula M(PR' YSpecifically hexachlorodisilane is reacted with PhMe Cl to give Pd{PPhMe(SiCl Cl and/ or Pd{PPhM62}3 Silyl complexes of platinum have beendescribed by I. Chatt et al., Journal of The Chemical Society A8 p.1343-1351 (1970). These materials were made by the reaction oftrihydrocarbyl silyl lithium with PtCl (PR the reaction of HSiCl withPtHCl(PPhMe and the reaction of triarylsilanes with PtCl (PMe Ph) thelatter in the presence of triethylamine. The reactions involve theformation of lithium chloride, H and triethylamine hydrochloriderespectively.

Applicants have devised a new method for the preparation of Pt and Pdcomplexes and have prepared new Pd complexes as shown below. Both theplatinum complexes and the new palladium complexes are useful ascatalysts for the hydrogenolysis of disilanes to form monosilanescontaining the SiH group and as catalysts of the reaction of hydrocarbonhalides with disilanes with the formation of a silicon-carbon bond as isdescribed and claimed in applicants copending application entitledTransition Metal Catalyzed Silylation, filed concurrently herewith Ser.No. 208,413.

This invention relates to the method of preparing silyl transition metalcomplexes com-prising reacting disilanes of the formula R Si Cl orhydrosilanes of the formula HSiR Cl with M (PR' Y at a temperature not"greater than 150 C. whereby compounds of the formula M(PR (SiR Cl Y areobtained in which R is a monovalent hydrocarbon radical of from 1 to 18carbon atoms, R is a monovalent hydrocarbon radical of from 1 to 10carbon atoms, n is an integer from O to 2, b is an integer from 0 to 1,M is Pd or Pt, Y is a halogen other than fluorine and m is an integerfrom 1 to 2.

The reactions involved in the method of this invention can berepresented schematically as follows:

ice

These reactions proceed when there is only one organic group on thesilicon or when there is no organic group on the silicon. Thus, thesilane reactants can be HSiCl HSiRCl Cl SiSiCl RClgSiSiRClg or RClSiSiCl The reaction is carried out by mixing the silanes and the metalphosphine complexes in any suitable container and heating at atemperature from at or below room temperature to C. Care should be takento keep moisture away from the SiM- complexes since this bond is easilyhydrolyzed with water especially under acidic conditions.

If desired, the reaction can 'be carried out in inert moisture-freesolvents such as benzene, toluene, petroleum ether and the like.

This invention also relates to new palladium complexes of the formulaPd(PR' (SiR Cl ),,,Y in which R is a monovalent hydrocarbon of 1 to 18carbon atoms,

R is a monovalent hydrocarbon radical of 1 to 10 carbon atoms,

Y is halogen other than fluorine,

c is an integer from 0 to 1, and

m is an integer from 1 to 2.

For the purpose of this invention R can be any monovalent hydrocarbonradical of from 1 to 18 carbon atoms such as alkyl radicals such asethyl, methyl, isopropyl, butyl, or octadecyl; alkenyl radicals such asvinyl, allyl or octadecenyl; cycloaliphatic radicals such ascyclopentyl, cyclohexyl, methylcyclohexyl, cyclohexenyl, cyclooctenyl,or cyclopentenyl; aralkyl radicals such as benzyl, beta-phenylpropyl orbeta-phenylethyl; aryl hydrocarbon radicals such as phenyl, xenyl,naphthyl, anthracyl, tolyl or xylyl.

For the purpose of this invention R can be any monovalent hydrocarbonradical of from 1 to 10* carbon atoms such as alkyl radicals such asmethyl, ethyl, isopropyl, or decyl; alkenyl radicals such as vinyl,allyl, or decenyl; cycloaliphatic radicals such as cyclopentyl,cyclohexyl, cyclohexenyl, methylcyclohexyl or methylcyclooctyl; aralkylradicals such as benzyl, 'beta-phenylethyl or betaphenylpropyl; and arylradicals such as phenyl, xenyl, naphthyl, tolyl or xylyl.

The following examples are illustrative only and should not be construedas limiting the invention which is properly delineated in the appendedclaims. The following abbreviations are used infra: Me for methyl, Phfor phenyl and Bu for butyl.

EXAMPLE 1 This example illustrates the reaction of disilanes with themetal phosphine complexes. In each case shown below the metal phosphinecomplex was dissolved in dry methylene chloride under nitrogen in theamounts specified and the disilane was slowly added thereto. Thereaction was allowed to proceed with stirring for the times andtemperatures specified. The solvent and byproducts were then removedunder vacuum and the remaining product washed with hexane and dried andthe structure was determined by infrared, mass spectrometry analysis andNMR.

TABLE Silane Moles Metal complexes Moles Reaction conditions ProductPd(PP11Mn)2Clz Room temp. for 1 hour Pd PPhMe SiCl G1. Pd(PPhMe );Clz---..do P l rnmeiiiisio Pd(PPhMez)zCl1 PhMez)z(SiMeCh)Cl Pd(PPhMe Cld(PPhMe:)n(SiMeCl Pt(PPhM62)zCla PPhM8:)3(SiC1a)Cl. GEPhMeDnChPtfilliyeflflswlh and Masher; 0. 425 Pd PPhMe.).o1, 0.107 70 c. for 16hours hMeMslcmcl' This run is given for comparison.

EXAMPLE 2 a silane of the formula HSiR Cl and M(PR' Y;. This exampleshows the reaction of hydrosilanes with A composition of matter of theformula the metal phosphine complexes. Following the procedure 7 ofExample 1 the reactions shown below were carried out in h PKPR3)2(S1RCl3')mY m giving the indicated products. w 10 TABLE Silanes MolesMetal complexes I Moles Reaction conditions Product HSiCl; 0.322Pd(PPhMez)aClz 0.1 0. for64hours Pd(PPhMe:)2(SiCl3)Cl. HMGSICI:.. 0.21Pd(PPhMea)zCl1 0. 09 -....do Pd(PPhMe1)1(SiMeO1;)C1. BS1013 0.17Pt(PPl1Mez)Ch 0.07 70 C.for 86 hours..- Pt(PPl1Me7)q(SiCl=)Cl. HMezSiCl0.234 Pd(PPhMe,),0u 0.102 50 0. for64hours.-.

This run is given for comparison only.

EXAMPLE 3 R is a monovalent hydrocarbon radical of from 1 to 18 When thefollowing disilanes are reacted with the folcarbon atoms l i p phosphinehalides in equal molar amounts, at R is a monovalent hydrocarbon radicalof from 1 to 10 50 C. in accordance with the procedure of Example 1, 30Carbon atoms,

the following products are obtained. 0 is an integer from 0 to 1,

TABLE Disilane Pd halide Product P11181101; PdBmPBua);Pd(SiPhCh)(PBua)1Br. (CeHu)zSi:lCl4- PdIflPBm): Pd(SiCsHnCh)( 3)IC3H5)1SlCl4.- Pdtmcmrhhhch P 1(sio.H.o1,)(P(0H,Ph).),01. rncnmsitclPdiPwHMenMe hCh Pd(SiCH;PhCh)(P(CHMe1)Me|hCl. (C1a a7)2$i:C1|PdlP(CaHa)alaClz Pd(Si 1aH:7C12)[ (C3 s)a}zCl- Me sigCltPd{P(C10Hz1)3}1C11 PMSIMQCh)( toHz1)a]zCl- (CiH9)1SiIC14-Pd{P(C6Hy)MGz]1C11 Pd(SiCnHoC1 )lP(C|Hn)Me)gCl.(MeCuHOrSizOhd(P(C|H4Me)Me:hCh P(1{Si (C|H4Me)Clz) P(COH4M)M:}IGI.(NaphthyDgSizCl Pd(PBua)aClz Pd Sr(na%hthyl)0h (PBus)aCl. (PhOsHmSizChPd[P(C 0Hz1)MezhCh Pd S1(C| 4P1 )C1z]{P(C10Hn)M8zhCl.

That which is claimed is: m is an integer from 1 to 2 and 1. The methodof preparing silyl transition metal com- Y is a halogen other thanfluoride. plexes comprising reacting disilanes of the formula 5. Acomposition of claim 4 of the formula ns zc mdz 5 0 6. A composition ofclaim 4 of the formula or hydrosilanes of the formula HS1R Cl withPd(PPhMe2)z(SiMeC12)C1 M(PR' Y; 7. A composition of claim 4 of theformula at a temperature not greater than 150 C. in the absencePd(PPhMe=)2(S1C13)= of an acid acceptor whereby compounds of theforrnula 3, A composition of d m 4 of the f l M(PR (S1R Cl Y areobtained in which P d zh (SiMe 2 R goangnonovalent hydrocarbon radlcalof 1 to 8 carbon References Cited R is a nionovalent hydrocarbon radicalof 1 to 10 carbon Chatt et al.: I.C.'S., A-8, pp. 134341, 1970. atoms,Chemical Abstracts, 67, 104719r, 1967. n is an integer from 0 to 2,Chemical Abstracts, 72, 132880h, 1970. b is an integer from 0 to 1,Chemical Abstracts, 72, 72225v, 1970. M is Pd or Pt, I Y is a halogenother than fluorine and DANIEL WYMAN. 'l' Examine! m is an integer from1 to 2.

2. The method in accordance with claim 1 in which SHAVER AsslstantExaminer the reactants are a disilane of the formula R Si Cl and 7 0M(PR,3)2Y2 US Cl XR 3. The method in claim 1 in which the reactants are260-4482 D, 448.2 E, 448.8 R

. PATENT OFFIC v UNITED STATES PATENT OFFICE CER'l'IFl'CA'lE OFCORRECTION Patent No. 5,7 j73 Dated: y 7, 975

It is certified that errors appear in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 5, line 59, in claim 1, 8" should read --l8-.

Column L, line 47, in claim l, fluoride should read -fluorine--.

Signed and sealed this 2nd day of April 19m.

(SEAL) Attest: I I

C. MARSHALL DANN EDWARD M.FLETCHER,JR. Atte sting Officer Commissionerof Patents

